Anthracene dye and process of making same.



. acids and alkalies, difficultly soluble in quino- UNlTElD %TATE% lPZAVll lEla lF HUGO WOLFF, OF LUDWIGSHAFEN-O'N-THE-RHINE, GERMANY, ASSIGNOR TO BADISGHE ANILIN & SODA FABRlK, OF L'UDWIGSHAFEN-ON-THE-RHINE, GERMANY, A CORPORA- TION.

ANTHRACENE DYE AND PROCESS OF MAKING SAME;

To all whom it may concern.-

Be it known that I, HUGO WoLFF, doctor of philosophy and chemist, subject of the Grand Duke of Baden, residing at Lu'dwigshafen-on-the-Rhine, Germany, have invented new and useful Improvements in Anthracene Dyes and Processes of Making the Same,'of which the following is a specification.

I have discovered that by treating amino derivatives of compounds containing a henzanthrone group, such for instance as hen-- zanthrone, benzanthrone quinolin, and de rivatives of these compounds, with a metallic salt, "or oxid, which acts as a condensing agent, such for instance as cuprous chlorid, ferric chlorid, and mercuric chlorid, mercuric oxid; cu rous oxid, cupric oxid, manganese dioxid, c romic acid, lead oxid, and lead peroxid, new coloring matters can be obtained which dye vegetable fiber from the vat very fast yellow, to brown-red, shades. Either one of these salts, or oxids, a mixture of two, or more, of them, may be used.

My new coloring matters are "characterized by being insoluble in water and in dilute lin yielding brown to brown-red solutions, soluble in concentrated sulfuric acid yielding from reddish brown to violet-blue solutions, and soluble in alkaline hydrosulfite solution yieldingolive-green to brown-red vats which dye unmordanted cotton yellow to violetbrown shades.

The following examples will serve to illustrate further the nature of my invention and the method of carrying it into practical effect, but the invention is not confined. .to these examples. The parts are by. weight.

Example 1. Boil together ten (10) arts of monoaminobenzanthrone (obtainab e by reducing the nitro compound described in example 1 of the specification of British Letters Patent No. 12,518/06), six (6) parts of anhydrous sodium acetate, four (4) parts of cuprous chlorid, and one hundred and fifty (150) parts of nitrobenzene. Vv hen a test portion shows that no unaltered aminobenzanthrone'is present, allow the mass to cool,

dilute with alcohol,'filter off the coloring matter and wash it first with. alcohol, then withhydrochloric acid, and finally with water.

The brown-yellow powder so obtained can be converted into' an olive-green paste by dissolving it in sulfuric acid and reprecipitating it with water. It is insoluble in water, di-

Specification of Letters Patent.

Application filed. March 12, 1908. Serial No. 4203M.

Patented m 1a, 1908.

cence in concentrated sulfuric acid; it is very difiicultly soluble in organic solvents yielding a yellowish brown solution. If, in this example, instead of aminobenzanthrone, a bromin derivative-thereof (obtainable for instance by treating aminobenzanthrone with bromin in lacial acetic acid solution) be em- 0 s w v ployed, a coloring matter is obtained pos sessing properties very similar to those hereinbefore described.

Example 2. Boil together for six (6) hours 1 ten (10) parts of diarninobenzanthrone (obtainable by reducing the nitro compound described in exam le 5 of the aforesaid British specification), fitteen (1'5) parts of anhydrous sodium acetate, four (a) parts of cuprous chlorid, and three hundred (300) parts of nitrobenzene. Dilute the cold reaction prodnot with alcohol, filter oil, and wash, and dry the coloring matter, whiclroonsists of a blackish brown powder having a metallic luster. In sulfuric acid it yields a violetblue non fluorescent solution. It is prac tically insoluble in most organic solvents. Quinolin dissolves traces of .it yielding a brown-red solution. With caustic soda and "hydrosulfite it yields a greenish brown vat which colors cotton olive-green, and these shades, on washing and drying, become brown-red.

Example 3. Boil together ten (10) parts of monoaminobenzanthronequinolin (obtainable by reducing the nitro compound described in example 3 of the aforesaid British specification), ten (10) parts of sodium acetate, four (a) parts of cnprous chlorid, and one hundred and fifty (15d) parts of naphthalene, until the amino compound is completely converted into coloring matter. Allow the reaction product to cool to about fifty (50) degrees centigrade and dilute with toluene; filter oil and wash and dry the coloring matter which separates out and which is a blackish brown powder which yields a dull green solution in concentrated sulfuric acid. It is very difi'icultly soluble in organic solvents; nitrohenzene and quinolin dissolve traces of it yielding brown/solutions. With caustic soda and hydrosulfite it yields a brownish red vat which colors cotton brown-red shades; which, on washing and drying, becomea beautiful brown. A similar coloring matter can be obtained from bromaminobenzanthronequinolin.

chlorid, and onehundred and fifty (150) -zanthrone is present;

parts of nitrobenzene, and work up the reaction product as described in the foregoing Example 1. The coloring matter consists of a dark brown paste, and, when dry, of a blackish brown owder which dissolves in concentrated sul uric acid yielding a redbrown solution with a dark green fluorescence. The new coloring matter is practically insoluble in organic solvents. With caustic soda and hydrosulfite it yields a redbrown vat which dyes vegetable fiber violetbrown.

Example 5. Boil together ten 10) parts of monoaminobenzanthrone, eight (8) parts of sodium acetate, four (4) parts of anhydrous ferric jchlorid, and one hundred and fifty (150) parts of nitrobenzene, until a test portion shows that no unaltered aminoben- Allow the mixture to cool, add alcohol, and filter off the coloring matter, which is similar to that obtained according to the foregoing Example 1..

Example 6. Boil together for five (5) hours, slx (6) parts of aminobenzanthronequinolin, six (6) parts of anhydrous sodium acetate, six (6) parts of mercuric chlorid,

and one hundred and fifty (150) parts of nitrobenzene, and then work up the mixture as described in the foregoing example 3. The coloring matter obtained is similar to that described in the said, example 3. I

Example 7. Boil together, for about six (6) hours, ten (10) parts of monoaminobenzanthrone (prepared by reducing the nitro compound obtained according to Example 1 of the specification of British Letters Patent No. 12,518/06), six (6) parts of cuprous oxid, and two hundred and fifty (250) parts of nitrobenzene. (hen the reaction mixture is cold add alcohol and filter off the coloring matter which separates out. It can be obtained in a pure state by dissolving it in sulfuric acid and precipitating by means of water and then extracting it with a solution of sodium hypochlorite. The coloring matter thus obtained yields, in concentrated sulfuric acid, a violet brown solution with a red-brown fluorescence, and dyes vegetable fiber from a vat fast yellow shades and 1s otherwise similar in its properties to the coloring matter obtained according to the foregoing Example 1.

the benzanthrone described in theforegoing Example 7; it dyes cotton-,brown-red shades and is otherwise similar to the coloring matter obtained according to the fore oing Example 2.

Example 9. Boil six (6) parts of monoaminobenzantl'lronequinolin (obtainable by reducing the nitro compound described in Example 3 of the aforesaid British specification) with six hundred (600) parts of glacial acetic acid, and add gradually, while boiling, a solution of four (4) parts of chromic acid in two hundred (200,) parts of glacial acetic acid. After from three (3), to four (4), hours, pour the mixture into a considerable quantity of water, filter off the coloring matter which separates out, wash. it with water and then extract it with boiling dilute sodium hypochlorite solution.

aste obtained dyes cotton, from the vat,

brown and is otherwise similar to the color-,

The reddish brown 1 nitric acid and reducing the trinitrobenzanthrone so obtained), two (2) parts of lead peroxid, and one hundred and fifty (150) parts of nitrobenzene. When the formation .of colorin matter is com lete, add alcohol to the coole mixture and ter 03 the colorin matter, wash it with alcohol and water, an then boil it with dilute nitric acid inorder .to extract any lead oxid present. The coloring matter thus obtained dyes cotton, from the vat, violet-brown and is otherwise similar to the coloring matter obtained according to the foregoing Example 4.

' Now what I claim is:

1. The process of producin coloring matter of the anthracene series I y treating an amino derivative of a. compound containing the benzanthrone grouping with a metallic salt or oxid which acts as a condensing agent.

2. The process of producin coloring mat-- ter of the anthraceneseries y treating an amino derivative of a compound containing grouping with cuprous chlorid.

3. The process of producing coloring matter of theanthracene series by treatin monoaminobenzanthrone with cuprous ch orid.

4. As new articles of manufacture the coloring matters 'of the anthracene series which can be obtained by treating an amino derivative of a compound containing the benzanthrone grouping with a metallic salt or oXid l which acts-as a condensing agent which coloring matters-are characterized by being insoluble in water and in dilute acids and alkalies, diflicultly soluble in quinolin yielding brown to brown-red solutions, soluble in concentrated sulfuric acid yielding from reddish brown to violet-blue solutions and soluble in alkaline hydrosulfite solution yielding olive-green to brown-red vats which dye unmordanted cotton yellow to violet -brown shades. I

5. As a new article of manufacture the coloring matter of the anthracene series which can be obtained by treating monoaminoconcentrated su benzanthrone With- 00. rous'chlorid, which coloring matter is inso uble in water and in dilute acids and alkalies, diflicultly soluble in quinolin yielding a brown solution, soluble in furic acid yielding a violetblue solution with a brown-red fluorescence and soluble in alkaline hydrosulfite solution yielding an olive-green vat which dyes unmordanted cotton yellow.

In testimony whereof I have hereunto set my hand in the presence of two subscribing witnesses.

HUGO WOLFF.

Witnesses:

J. Auto; LLoYD, 'ERNEsT G. EHRHARDT. 

